Polyoxypropylene-benzenesulfonamides



Patented Dec. 4, 1 951 POLYOXYPROPYVLENE-BENZENEV- SULFONAMIDES Lester G. Lundsted, Grosse Ile, Mich., assignor to Wyandotte Chemicals Corporation, Wyandotte, Mich., a corporation of Michigan No Drawing. Application April 9, 1949,

' Serial No. 86,588

, g 1 The present invention relates to a new type of nitrogen substituted aryl sulfonamides, in which 14 Claims. (Cl. 260556) one amide hydrogen atom is replaced with one or more oxyalkylene groups or in which both amide hydrogen atoms are replaced with one or more oxyalkylene groups. The compounds of my invention may be alternatively defined as N- polyoxyalkylene aryl sulfonamides, wherein the aryl group is derived from benzene and it lower aliphatically C-substituted homologues, such as-- toluene; xylene, mesitylene, durene, ethylbenzene,

cumeneand cymene. These new compounds core respondto the following type formula:

Ar-SOa-N where-' v Ar is an aromatic radical of the benzene series.

R1 is a lower alkyl, monooxyalkylene or poly-oxyalkylene, and

R2 is a monooxyalkylene or polyoxyalkylene.

Compound of my invention wherein N-polyoxyalkylene groups are present have been found tobe particularly valuable in possessing low melt- :ing points and low volatility at elevated tempera-' tures. They are illustrated by the following type Preferably, the lower alkyl group in the above stated formulae is one containing up t 4 carbon atomsand derived from either a straight or and the oxyalkylene, group is preferably polyoxypropylene, present in branched chain alkane;

the amount 2-8 propenoxy groups. (The term polyoxypropylene as herein employed in both the specification and claims refers of course to a group having an acyclic chemical structure and a terminal hydroxyl radical.) The new compounds of my invention are par- 'ticularly suitable as plasticizing agents for synthetic resins, especially resins of the vinyl type.

In the search for synthetic resin plasticizing compounds, it has generally been the objective drophobic,

[to obtain the following desired physical properties: Y. (1) High resistance to moisture, which necessarily means that the compound be strongly hy- (2 High heat stability, which means that the-..

compound be of relatively low volatility, and

(3) Liquid at normal temperatures.

Referring more specifically to the N-alkyl benzenesulfonamides ofthe prior art (Beilstein, vol. 11, pp. 39-42, 1928) it will be seen, for example, that mono-N-ethyl benzenesulfonamide is a p solid having a melting point of 57-58 C. and that it is soluble in weakly alkaline aqueous solution. And even 'where the substituent is an N- alkoxyalkyl group, the resultant compound, such as mono-methoxypropyl toluene sulfonamide, is soluble in dilute NaOH solution and of normally solid form. of. U. S. Pat.No. 2,071,917. So also, is mono-Nn butyl toluenesulfonamide a solid having a melting point of 42-43 C.

, However, when the replaceable hydrogen atom on the nitrogen atom of mono-N-ethyl benzenesulfonamide, for example, is substituted with an oxyalkylene group, such as a polyoxypropylene group, the resultant compound is found to be a liquid at normal temperatures, which liquid is strongly hydrophobic and capable of being heated to temperatures on the order of 170 C. under 5 millimeters of Hg pressure without distillation or decomposition.

The achievement of such properties in the compounds of my invention is particularly unusual and unexpected when it is considered that the lower alkylene oxides and gylcols themselves are quite readily water-soluble; and that the alkylene oxide condensation or modification of other benzenesulfonamides, such as the oleyl-benzenesulfonamide of U. S. Pat. No. 2,131,142, modified with ethylene oxide, produces a compound which Example 1v In a 2 liter 3-neck round bottom flask fitted rwith a mechanical stirrer working through-a packing gland, a reflux condenser topped by a Dry Ice condenser connected toa mercury blowofi valve, a thermometer and a capillary inlet for oxide feed, there was'placed 740 grams of N-ethyl benzenesulfonamide and 0.2; Weight percent of sodium hydroxide based on the weight of amide. The stirrer was started and heat applied tothe mixture while a stream of nitrogen was passed through the flask to displace air. When the temperature reached 160 C. the nitrogen feed was removed and a reservoir of propylene oxide connected to the capillary feed line. The nitrogen in the reaction flask was displaced withpropylene oxide vapor and then the addition of propylene oxide continued at the rate atwhich reaction took place. A total of 879.9 grams of propylene oxidewas added to the reaction mixturein the course of 11.8 hours while the temperature was maintained at an average temperature of 150 C.

3 The average rate of additiori'or the propylene oxide corresponds to 0.32mol per mol of amide per hour. This corresponded to a total addition of 3.8 mols of propylene oxide per mol of N-ethyl 4 up in the same'manneras in Examplel except that the catalyst was neutralized with 50% sulfuric acid. The product weighed 3982 grams, corresponding to a yield of 95.5% based on the benzenesulfonamide. At the conclusion of the 5 weight of thestarting materials. The deterreaction the propylene oxide feed was replaced mined molecular weight of the product by nitrowith a stream of nitrogen and the reaction mixgen analysis was 402, as compared to a calculated ture cooled toroom temperature. The sodium molecular weight of 417. hydroxide catalyst was neutralized by bubbling Example 4 carbon dioxide gas into the mixture after which the product was heated to 170 C. at approxi- A 0 L rocking b ty r a t s mately 10 mm. to remove volatile materials. Charged h'3 grams ofbenzeneslllfonamide The residue was filtered hot to yield 1535.3 grams d .2 by weight (amide bas s) f aust c (94.8%) of a product having a molecular Weight a- Af displa of the air in the autoof 384 by nitrogen determination, the theoretical l5 Ola-VB and heating to 9349 grams of ethylmolecular weight, based on the amount of p-ropylene Oxide (corresponding to 1. 6 mole per mel of one oxide addition, being 405. a d wa pumpe n at s -a to main- Emmp-le tain a pressure of 15-75 p. s. i. gauge. The ethyl- V ene oxide was added over a period of 1 hour and The reaction was carried out as in Example 1 5 minutes. The product weighed 3752 grams but N-ethyl benzencsulfonami'de was replaced by corresponding to a 92% yield. The molecular benzenesulfonamide. From 314 grams of benweight of the product was found to be- 322 by zenesulfonamide and 998.2 grams of propylene hydroxyl number determination and 203 :by oxide (corresponding to 3.1 mole per mol of bennitrogen analysis, the calculated molecular Zenesulfonamide), in the presenceof 0.57 Weight Weight bein percent of sodium hydroxide based on the amide, Example 5- I at an average temperature of 150 (1., there was obtained 1196.3 grams (91.2%) of a product The.1eacmn was earned out'as m m showing a molecular Weight of 635 on the basis but using 157.2 grams of benzenesulfonamide in of nitrogen analysis, the calculated molecular Place of the L'ethyl benzenesulfcgtamlde' weight, based on the amount of propylene oxide 781 grams of propylene (cone addition, being 656. The product was not vola- 5901mm? to m per 9} of amid?) was me at and 5 of mercury pressure. added at an average temperature of 185 C. to It was not soluble in aqueous alkaline solution, produce 8203 grams of P product thus indicating that both hydrogen atoms on the was three tunes Wlth approximately equal nitrogen had been replaced and that the comquanmles of -wat?r.and t dehydratedfunder pound was a N N di polyoxypmpylene bgnzene vacuum. After this treatment the product gulfonamida showed .a molecular weight of 788 by..n1trogen Example 3 analysls and 740 by hydroxyl number determina- 4 q v tion; the calculated molecular weight being 938. A two gallon stainless steel autoclave was 40 ,From the foregoing examples, it will be seen charged with 1850 gram f N y n that excellent yields as well as a highly efficient .sulfonamlde and e t p c nt of sodium degree of condensation (determined molecular hydroxide based on the amideweights as compared to calculated molecular p a d y nitrogen. the autoclave sealed and weights) are obtained by my process of synthesizheated to 145 C. A totalof 2320 g ams f ing the alkylene. oxide modified aryl sulfonapropylene oxide (corresponding to 4.0 ,mols per mides. mol of amide) was pumped into the reaction at Variation in the amount of propylene oxide such a rate as to maintain an average pressure of substituted in the aryl sulionamides is further 18 p. s. i. gauge. At the conclusion-of the reacillustrated by the following examples, which are tion, when the pressure had dropped to zero, the '50 here set forth in tabular formfor the purpose product in the autoclave was blown and worked of convenience in description:

Crude Product Molecular Weight I starting NaOH Average r Material: Weight it?!" ti w ei lft'" 1 35? 53:52:22 r2515 Galcu- From ample g grams Oxide, g. OxideflH Per ent tion, hrs. Mols/ G." Per latedfrom Found Per oiAinide Mol/hr. Cent Oxide OK No. Cent Added N PROPYLENE OXIDE-MODIFIED BENZENESULFONAMIDES 785 735 2.54 0.25 15:41 0.16 175 1,490 98 304 359 314 185 143.5 2. 0.27 1:12 2.08 141-194 317:8 97 328.5 353 sis 213 232 4.0 1 mo 1. 42 143 441.7 99.4 445 379 4 53.3 33.8 2.32 0.37 1:55 1. 22 -145 87 100 388 not analyzed PROPYLENE OXIDE-MODIFIED HOMOLOGUES or BENZENESULFONAMIDE 10..-. p-xylene sul- 100 125.5 4.0 1 5:45 0. 595 225.5 99.3 417 392 400 fonamide. 11.-.- p-toluene sul- 171 232 4 1 4:20 0. 925 154 405 100 403 320 411a fonamide. 12.--. N-ethyl 0-, p- 201 174 s 1 2:40 1.124 152 373 99.6 375 4351 ---.412

toluene sulfoiiamide.

News: ,All reactions carried outat atmospheric pressure.

It will be noted from the data in the foregoing tabular form of examples, that from 0.21% of NaOH catalyst (on the basis of amide present) to 2.28% is operable in the synthesizing process; and the temperature of the reaction is preferably in the range of 115-185 C.

Other alkylene oxide condensation catalysts may be employed such as other caustic alkalis, sodium alcoholates, and amines.

It is well known that the theoretical or calculated molecular weights of alkylene oxide addition and condensation products vary greatly from those determined by analysis, and often according to the particular method of analysis. It will be noted, however, from the data hereinabove given in Examples 1-12, that the molecular weights as determined by the alternative hydroxyl number and nitrogen analyses were in exceptionally close agreement with the theoretical value calculated on the basis of starting materials. Thus, in all cases except Example 5, (wherein the highest amount of propylene oxide was added) the respective analytical molecular weight values either bracketed the calculated value or the nitrogen analysis value was within plus or minus 7% of the calculated value. This latter observation further testifies to the high efficiency of the reaction of my invention.

Other modes of applying the principle of my invention may be employed, changes being made as regards to the details described, provided the features stated in any of the following claims or the equivalent of such be employed.

I, therefore, particularly point out and distinctly claim as my invention:

1. N,N di-polyoxypropylene amide.

2. N-ethyl, fonamide.

benzenesulfon- N-polyoxypropylene benzenesul- 3. N-mono n-butyl, N-polyoxypropylene ben- 4 where- Ar is an aromatic hydrocarbon radical of the group consisting of benzene and alkyl substituted benzene containing up to a total of 4 5 carbon atoms in the alkyl portion,

R1 is selected from the group consisting of lower alkyl and polyoxypropylene, and R2 is polyoxypropylene.

7. N-ethyl, N-polyoxypropylene benzenesulfonamide wherein the polyoxypropylene group contains an average of from 1-13.5 oxypropylene groups.

8. N-mono, n-butyl, N-polyoxypropylene benzenesulfonamide wherein the polyoxypropylene group contains an average of from 1-13.5 oxypropylene groups.

9. Compounds as defined in claim 1 wherein the polyoxypropylene groups together contain a total of from 2-27 oxypropylene groups.

10. Compounds as defined in claim 1 wherein the polyoxypropylene groups together contain a total of from 4-16 oxypropylene groups.

11. N-ethyl, N-polyoxypropylene p-toluenesulfonamide.

12. Compounds as defined in claim 11 wherein the polyoxypropylene group contains from 2-8 oxypropylene groups.

13. N,N-di-polyoxypropylene p-xylenesulfonamide.

14. Compounds as defined in claim 13 wherein the polyoxypropylene groups together contain a total of from 4-16 oxypropylene groups.

LESTER G. LUN'DSTED.

REFERENCES CITED The following references are of record in the file of this patent: I

UNITED STATES PATENTS Name Date Orthner et al May 18, 1935 0 Number Moss Dec. 6, 1938 Ulrich et a1. Jan. 23, 1940 De Groote Mar. 28, 1944 FOREIGN PATENTS Country Date Great Britain -2 Sept. 12, 1932 Great Britain Dec. 3, 1934 France Mar. 27, 1936 Switzerland June 1, 1945 Germany Sept. 28, 1939 Number Albrecht Sept. 21, 1937 

6. ALKYLENE OXIDE-MODIFIED ARYL SULFONAMIDES OF THE TYPE FORMULA: 